Thiazoleazo dyes having a diazo component from the isothiazole or thiadiazole series

ABSTRACT

Thiazoleazo dyes of the formula ##STR1## where X is nitrogen or a radical C--R 5 , R 5  being cyano, halogen, alkoxycarbonyl or thiocyanato, R 1  is cyano, chlorine, unsubstituted or substituted C 1  -C 6  -alkyl, unsubstituted or substituted phenyl, unsubstituted or substituted thienyl, unsubstituted or substituted pyridyl or unsubstituted or substituted alkylthio, alkylsulfinyl or alkylsulfonyl, R 2  is unsubstituted or substituted alkyl, cycloalkyl, unsubstituted or substituted phenyl, furyl, unsubstituted or substituted thienyl or pyridyl and R 3  and R 4  independently of one another are each unsubstituted or substituted alkyl, or R 3  and R 4 , together with the nitrogen atom which links them, form a heterocyclic radical, are used for dyeing textile fibers having good wet fastness and color build-up.

The present invention relates to novel thiazoleazo dyes of the formula I ##STR2## where X is nitrogen or a radical C--R⁵, R⁵ being cyano, halogen, C₁ -C₄ -alkoxycarbonyl or thiocyanato, R¹ is cyano, chlorine, unsubstituted or substituted C₁ -C₆ -alkyl, a radical of the formula Y(CH₂)_(m) S(O)_(p) --, Y being hydrogen, cyano or C₁ -C₄ -alkoxycarbonyl, m being 1 or 2 and p being 0, 1 or 2, a radical of the formula R⁶ (--OC₂ H₄)_(n), R⁶ being C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkyl, benzyl or phenyl and n being 1, 2, 3 or 4, unsubstituted or substituted phenyl, thienyl, C₁ -C₄ -alkylthienyl, pyridyl or C₁ -C₄ -alkylpyridyl, R² is C₁ -C₈ -alkyl, phenoxy-substituted C₁ -C₄ -alkyl, C₅ -C₇ -cycloalkyl, unsubstituted or substituted phenyl, furyl, thienyl, C₁ -C₄ -alkylthienyl, halothienyl or pyridyl, R³ is C₁ -C₆ -alkyl, C.sub. 1 -C₆ -alkyl which is substituted by cyano or phenyl, C₃ -C₁₂ -alkyl whose alkyl chain is interrupted by from 1 to 4 oxygen atoms and may be substituted by phenyl or phenoxy, or C₁ -C₄ -alkoxy and R⁴ is C₁ -C₆ -alkyl or C₃ -C₁₂ -alkyl whose alkyl chain is interrupted by from 1 to 4 oxygen atoms and may be substituted by phenyl or phenoxy, or R³ and R⁴, together with the nitrogen atom which links them, form a 5-membered or 6-membered saturated heterocyclic radical which may contain further heteroatoms, with the proviso that R³ and R⁴ are simultaneously C₁ -C₆ -alkyl only when R¹ has one or more oxygen atoms or is a radical NC(CH₂)_(m) S(O)_(p) --, m and p each having the abovementioned meanings, and their use for dyeing textile fibers.

DE-A-2 910 806 and JP-A-151 653/1982 disclose azo dyes which have a thiazole derivative as a coupling component. Furthermore, earlier patent applications DE-A-3 810 643 and DE-A-3 816 698 disclose thiazoleazo dyes having a diazo component from the isothiazole series.

It is an object of the present invention to provide novel thiazoleazo dyes which have a diazo component from the isothiazole or thiadiazole series and possess advantageous performance characteristics.

We have found that this object is achieved by the thiazoleazo dyes of the formula I which are defined in detail above.

All alkyl groups occurring in the abovementioned formula I may be either straight-chain or branched.

R¹, R², R³ and R⁴ are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or isohexyl.

R¹ is furthermore, for example, CH₃ OC₂ H₄, C₂ H₅ OC₂ H₄, C₆ H₅ CH₂ OC₂ H₄, C₆ H₅ OC₂ H₄, CH₆ H₁₁ OC₂ H₄, CH₃ (OC₂ H₄)₂, C₂ H₅ (OC₂ H₄)₂, C₆ H₅ (OC₂ H₄)₂, C₆ H₅ (OC₂ H₄)₂, C₆ H₁₁ (OC₂ H₄)₂, CH₃ (OC₂ H₄)₃, C₂ H₅ (OC₂ H₄)₃, C₆ H₅ CH₂ (OC₂ H₄)₃, C₆ H₅ (OC₂ H₄)₃, C₆ H₁₁ (OC₂ H₄)₃, CH₃ (OC₂ H₄)₄, C₂ H₅ (OC₂ H₄)₄, C₆ H₅ CH₂ (OC₂ H₄)₄, C₆ H₅ (OC₂ H₄)₄ or C₆ H₁₁ (OC₂ H₄)₄.

R² is furthermore, for example, cyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl, cycloheptyl, phenoxymethyl, 2-phenoxyethyl, 2- or 3-phenoxypropyl, 2- or 4-phenoxybutyl, heptyl, octyl or 2-ethylhexyl.

If R¹ is substituted C₁ -C₆ -alkyl, suitable substituents are, for example, C₁ -C₄ -alkoxy, phenoxy, phenyl which may be substituted by C₁ -C₄ -alkyl, halogen, in particular fluorine, chlorine or bromine or C₁ -C₄ -alkoxy, or are C₁ -C₄ -mono- or dialkylcarbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl, morpholinocarbonyl, piperazinocarbonyl, N-(C₁ -C₄ -alkyl)-piperazinocarbonyl, phenylthio, phenylsulfonyl, anilino, C₁ -C₄ -alkanoylamino, benzoylamino, N-(C₁ -C₄ -alkyl)-N-(C₁ -C₄ -alkanoyl)-amino, N-(C₅ -C₇ -cycloalkyl)-N-(C₁ -C₄ -alkanoyl)-amino, N-phenyl-N-(C₁ -C₄ -alkanoyl)-amino,N-(C₁ -C₄ -alkyl)-N-benzoylamino,N-phenylN-benzoylamino, phenylsulfonylamino, N-(C₁ -C₄ -alkyl)-N-phenylsulfonylamino, N-phenyl-N-phenylsulfonylamino, N,N'-(C₁ -C₄ -dialkyl)-ureido, N-phenyl-N'-(C₁ -C₄ -alkyl)ureido, N,N'-diphenylureido, morpholino or a radical of the formula ##STR3##

R¹ is furthermore, for example, phenyl which is unsubstituted or substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, in particular fluorine, chlorine or bromine, hydroxyl, phenoxy, phenylthio, phenylsulfonyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -hydroxyalkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -(pyrrolidino)-, -(piperidino)-, -(morpholino)-, -(piperazino)- or -[N-(C₁ -C₄ -alkyl)-piperazinoalkyl], C₁ -C₄ -phenylalkoxy, C₁ -C₄ -dialkylsulfamoyl or C₁ -C₄ -alkanoylamino, or is styryl which is unsubstituted or substituted by C₁ -C₄ -dialkylamino, or is methylthio, ethylthio, 2-(methoxycarbonyl)-ethylthio, 2-(ethoxycarbonyl)-ethylthio, 2cyanoethylthio, methylsulfinyl, ethylsulfinyl, 2-(methoxycarbonyl)-ethylsulfinyl, 2-(ethoxycarbonyl)ethylsulfinyl, 2-cyanoethylsulfinyl, methylsulfonyl, ethylsulfonyl, 2-(methoxycarbonyl)-ethylsulfonyl, 2-(ethoxycarbonyl)-ethylsulfonyl or 2-cyanoethylsulfonyl.

If R¹ or R² is substituted phenyl, suitable substituents are, for example, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano, halogen, in particular chlorine or bromine, C₁ -C₄ -alkanoylamino, sulfamoyl and C₁ -C₄ -mono- and dialkylsulfamoyl, where the alkyl chain may be interrupted by an oxygen atom.

R⁵ is, for example, fluorine, chlorine, bromine, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl.

R³ and R⁴ together with the nitrogen atom which links them, are, for example, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino or N-(C₁ -C₄ -alkyl)piperazino, such as N-methyl- or N-ethylpiperazino.

R³ and R⁴ are furthermore, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 2- or 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 1,3,6,9-trioxaundecy1,3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxatetradecyl, 3-benzyloxypropyl or 6-phenoxy-4-oxahexyl.

R³ is furthermore, for example, 2-cyanoethyl or 1- or 2-phenylethyl.

Preferred thiazoleazo dyes of the formula I are those in which X is a radical C--R⁵, where R⁵ has the abovementioned meanings.

Particularly preferred thiazoleazo dyes of the formula I are those in which X is a radical C--R⁵, where R⁵ is cyano.

Particularly preferred thiazoleazo dyes of the formula I are those in which R¹ is unsubstituted or substituted phenyl or a radical of the formula R⁶ (--OC₂ H₄)_(n), where R⁶ is C₁ -C₄ -alkyl, cyclohexyl, benzyl or phenyl and n is 1, 2 or 3, R² is cyclohexyl, unsubstituted or methoxy substituted phenyl or thienyl, R³ is C₁ -C₄ -alkyl, R⁴ is C₃ -C₉ -alkyl whose alkyl chain is interrupted by from 1 to 3 oxygen atoms and may be substituted by phenoxy, and X is C--CN.

Particularly noteworthy thiazoleazo dyes of the formula I are those in which R¹ is unsubstituted or substituted phenyl or a radical of the formula R⁶ (--OC₂ H₄)_(n), where R⁶ is phenyl and n is 2.

Further particularly noteworthy thiazoleazo dyes of the formula I are those in which R⁴ is C₁ - or C₂ -alkoxyethyl, C₁ - or C₂ -alkoxypropyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,7-dioxaoctyl, 4,7-dioxanonyl or 6-phenoxy-4-oxahexyl.

The novel thiazoleazo dyes are prepared in a conventional manner. For example, a 5-aminoisothiazole derivative of the formula ##STR4## where R¹ and R⁵ each have the abovementioned meanings, or a 5-aminothiadiazole derivative of the formula III ##STR5## where R¹ has the abovementioned meanings, can be diazotized and the product coupled with a thiazole of the formula IV ##STR6## where R², R³ and R⁴ each have the abovementioned meanings.

5-Aminoisothiazoles of the formula II are known and are described in, for example, earlier patent application DE-A-3 804 394, and can be obtained by a method similar to the preparation process described there.

5-Aminothiadiazoles of the formula III are likewise known and are described in, for example, R. C. Elderfield, Heterocyclic Compounds, Vol. 7, John Wiley, New York, 1961, and can be obtained by a method similar to the methods stated there.

The thiazoles of the formula IV are in general also known compounds. They are described, for example, in U.S. Pat. No. 3 770 719 or in J. V. Metzger, Heterocyclic Compounds --Thiazole and its Derivatives, Vol. 34, Part 1, Interscience Publ., John Wiley, New York, 1979, or can be obtained by a method similar to the methods stated there.

The Examples give further details on the preparation of the novel dyes.

In general, the novel dyes of the formula I which have 5 or more oxygen atoms in the radicals R³ and R⁴ together are in the liquid state at room temperature.

The novel thiazoleazo dyes of the formula I can advantageously be used as disperse dyes for dyeing textile fibers, in particular cellulose esters or polyesters, as well as polyamides or blended fabrics of polyesters and cellulose fibers.

Dyeings having good wetfastness are obtained

To achieve an advantageous build-up of color, it may be advantageous in some cases to use mixtures of the novel dyes of formula I for dyeing.

The Examples which follow illustrate the invention. Examples 1 and 2 describe the preparation of the coupling component.

EXAMPLE 1

98 g of sodium thiocyanate were added to 300 ml of toluene, 100 ml of water and 5 g of a phase transfer catalyst. Thereafter, 181 g of thiophene-2-carbonyl chloride were added dropwise in the course of 1 hour and the mixture was stirred for 5 hours at from 20° to 25° C. The pH of the suspension was kept at 6-7. 168 g of bis(2-methoxyethyl)-amine were then added dropwise at from 20° to 25° C. in the course of 1 hour, after which the pH was corrected to 7-7.5 and stirring was continued overnight. 350 ml of water and 200 g of sodium hydroxide solution (50% by weight) were then added, and 124 g of chloroacetic acid were introduced at not more than 40° C. The mixture was then stirred for 5 hours with evaporative cooling. After the end of CO₂ elimination, the aqueous phase was separated off and the organic phase was extracted twice by shaking with water. The organic phase was subjected to distillation under reduced pressure (bath temperature: not more than 155° C.). 250 g of the coupling component of the formula ##STR7## were obtained as a brown oil.

EXAMPLE 2

The procedure described in Example 1 was followed; except that, instead of thiophene-2-carbonyl chloride, 170 g of benzoyl chloride were used. 240 g of the coupling component of the formula ##STR8## were obtained as a viscous, greenish oil, which rapidly solidified to give a colorless, crystalline product of melting point 47° C.

EXAMPLE 3

13.8 g of 3-(2-methoxyethyl)-4-cyano-5-aminoisothiazole were dissolved in 160 ml of glacial acetic acid and 35 ml of propionic acid. The solution was then cooled to 0°-5° C., and 32 g of 42% strength by weight nitrosylsulfuric acid were added dropwise at this temperature, and stirring was carried out for 3 hours. The mixture was then poured into a solution of 29.7 g of the thiazole of the formula ##STR9## and 200 g of glacial acetic acid, 40 g of propionic acid and 30 ml of aqueous 10% strength by weight amidosulfonic acid solution. The mixture was then cooled to 0°-5° C. The coupling reaction took place immediately. The mixture was kept stirrable by adding about 800 ml of ice water and 200 g of ice. After the mixture had been buffered at pH 0-0.5 with sodium acetate, the precipitated dye of the formula ##STR10## was filtered off under suction, washed with water and dried to give 47 g of a dark red to violet powder which dissolves in N,N-dimethylformamide to give a reddish blue solution and dyes polyethylene terephthalate fabric in reddish blue to navy hues.

λ_(max) 580 nm (9 : 1 v/v N,N-dimethylformamide/ glacial acetic acid).

EXAMPLE 4

13.8 g of 3-(2-methoxy-ethyl)-4-cyano-5-aminoisothiazole were diazotized similarly to Example 3 and the product was coupled with 27.9 g of the thiazole of the formula ##STR11## to give 48 g of a dark red powder of the formula ##STR12## which dissolves in acetone to give a violet solution and dyes polyethylene terephthalate fabric in violet hues with excellent lightfastness. The dye has very good build-up properties.

λ_(max) : 554 nm (9 : 1 v/v N,N-dimethylformamide/ glacial acetic acid).

EXAMPLE 5

17.2 g of 3-methyl-4-thiocyanato-5-aminoisothiazole were dissolved in 220 g of glacial acetic acid and 48 g of propionic acid at about 45° C. The solution was then cooled to 0°-5° C., 32 g of 42% strength by weight nitrosylsulfuric acid were added at this temperature and stirring was carried out for 3.5 hours at from 0° to 5° C. The resulting solution was added to a mixture of 29.2 g of 2-bis-(2-methoxyethyl)-amino-4-phenylthiazole, 50 g of glacial acetic acid and 10 g of an aqueous 10% strength by weight amidosulfonic acid solution. 8 g of concentrated hydrochloric acid and 400 g of ice water were also added and the mixture was cooled to 0° C. with ice. The coupling mixture was buffered at pH 0.8-1 with dilute sodium acetate solution. The precipitated dye of the formula ##STR13## was filtered off under suction, washed and dried to give 42 g of a reddish violet powder which dissolves in N,N-dimethylformamide to give a violet solution and dyes polyethylene terephthalate in strong dull bluish red to violet hues.

λ_(max) : 542 nm (9 : 1 v/v N,N-dimethylformamide/ glacial acetic acid).

EXAMPLE 6

20.7 g of 3-(thien-3-yl)-4-cyano-5-aminoisothiazole were sprinkled into a mixture of 125 g of sulfuric acid (71% strength by weight), 22 g of glacial acetic acid and 32 g of nitrosylsulfuric acid (42% strength by weight), cooled to 0° C. The diazotization mixture was stirred for 4 hours at from 0° to 5° C., and a yellow suspension was obtained. This mixture was combined at <8° C. with a solution, cooled to 0°-5° C., of 42.4 g of the thiazole of the formula ##STR14## in 300 g of glacial acetic acid, 50 g of propionic acid, 50 g of ice and 1 g of amidosulfonic acid. During introduction of the diazonium salt, a little ice and ice water were added simultaneously so that the mixture remained stirrable. Stirring was continued for 10 minutes at about 0° C., after which the mixture was buffered at pH 0.2-0.4 with dilute, ice-cold sodium hydroxide solution. The dye of the formula ##STR15## was isolated similarly to Example 5. It dissolves in N,N-dimethylformamide to give a solution having a navy hue and dyes polyethylene terephthalate in strong, blue hues. λ_(max) : 588 nm (9 : 1 v/v N,N-dimethylformamide/ glacial acetic acid).

The dyes listed in Tables 1 to 4 below are obtained in a similar manner.

                                      TABLE 1                                      __________________________________________________________________________      ##STR16##                                                                     Example                                                                        No.  R.sup.1                                                                               R.sup.2                                                                               R.sup.3                                                                               R.sup.4   Hue                                        __________________________________________________________________________      7   C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.2 OCH.sub.3                                                      violet                                      8   C.sub.2 H.sub.5 OC.sub.2 H.sub.4                                                      C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                bluish red                                  9   C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               violet                                     10   C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                       C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               violet                                     11   C.sub.6 H.sub.5                                                                       C.sub. 6 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                                       violet                                     12   C.sub.6 H.sub.5                                                                        ##STR17##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                       reddish blue                               13   C.sub.6 H.sub.5                                                                        ##STR18##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                                       reddish blue                               14   C.sub.6 H.sub.5                                                                        ##STR19##                                                                            C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                                       reddish blue                               15   C.sub.6 H.sub.5                                                                        ##STR20##                                                                            C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               reddish blue                               16   C.sub.6 H.sub.5                                                                        ##STR21##                                                                            C.sub.3 H.sub.7 (n)                                                                   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               reddish blue                               17                                                                                   ##STR22##                                                                             ##STR23##                                                                            C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                                       blue                                       18                                                                                   ##STR24##                                                                             ##STR25##                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                       reddish blue                               19                                                                                   ##STR26##                                                                             ##STR27##                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                                       reddish blue                               20                                                                                   ##STR28##                                                                             ##STR29##                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                                       reddish blue                               21                                                                                   ##STR30##                                                                             ##STR31##                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                       blue                                       22                                                                                   ##STR32##                                                                             ##STR33##                                                                            C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                       blue                                       23                                                                                   ##STR34##                                                                             ##STR35##                                                                            C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                                       blue                                       24                                                                                   ##STR36##                                                                             ##STR37##                                                                            C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               blue                                       25   (CH.sub.3).sub.2 CH                                                                    ##STR38##                                                                            C.sub.3 H.sub.7 (n)                                                                   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               navy                                       26   C.sub.2 H.sub.5 OC.sub.2 H.sub.4                                                       ##STR39##                                                                            C.sub.3 H.sub.7 (n)                                                                   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               navy                                       __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR40##                                                                     Example No.                                                                           R.sup.1                                                                               R.sup.3                                                                               R.sup.4   R.sup.5                                                                            Hue                                         __________________________________________________________________________     27     CH.sub.3                                                                              C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                CN  reddish blue                                28     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                CN  reddish blue                                29     C.sub.3 H.sub.7 (n)                                                                   C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                CN  reddish blue                                30     (CH.sub.3).sub.2 CH                                                                   C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                CN  reddish blue                                31     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.3 H.sub.6 OCH.sub.3                                                                CN  navy                                        32     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         CN  navy                                        33     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         CN  navy                                        34     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                CN  navy                                        35     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OCH.sub.3                                                                CN  navy                                        36     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               CN  navy                                        37     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                        CN  navy                                        38     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                       CN  navy                                        39     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.3 H.sub.7 (n)                                                                   (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                       CN  navy                                        40     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.3 H.sub.7 (n)                                                                   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               CN  navy                                        41     CH.sub.3                                                                              C.sub.2 H.sub. 5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               SCN bluish violet                               42     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               SCN bluish violet                               43     CH.sub.3                                                                              C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                SCN bluish violet                               __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR41##                                                                     Example No.                                                                           R.sup.1                                                                               R.sup.3                                                                               R.sup.4   Z   Hue                                         __________________________________________________________________________     44     CH.sub.3                                                                              C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                H   violet                                      45     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                H   violet                                      46     (CH.sub.3).sub.2 CH                                                                   C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                H   violet                                      47     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                H   violet                                      48     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                Cl  violet                                      49     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.5                                                                          H   violet                                      50     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                               H   violet                                      51     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                               Cl  violet                                      52     CH.sub.3 OC.sub.2 H.sub.4                                                             CH.sub.3                                                                              C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                               H   violet                                      53     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                      C.sub.2 H.sub.4 OCH.sub.3                                                                H   violet                                      54     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                      CH.sub.3  H   violet                                      55     CH.sub.3 OC.sub.2 H.sub.4                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                                OCH.sub.3                                                                          bluish violet                               56     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                                OCH.sub.3                                                                          bluish violet                               __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR42##                                                                     Example                                                                        No.  R.sup.1   R.sup.2                                                                               R.sup.3                                                                               R.sup.4 R.sup.5                                                                            Hue                                   __________________________________________________________________________     44   CH.sub.3  C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              H   red                                   45   CH.sub.3  C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              Cl  red                                   46   CH.sub.3  C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              Br  red                                   47   CH.sub.3  C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              SCN violet                                48   CH.sub.3  C.sub.6 H.sub.5                                                                       C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              SCN violet                                49   C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.5                                                                       C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              CN  violet                                50   C.sub.6 H.sub.5                                                                           ##STR43##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              CN  reddish blue                          51   C.sub.6 H.sub.5                                                                           ##STR44##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              SCN reddish blue                          52   CH.sub.3                                                                                  ##STR45##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              SCN reddish blue                          53   CH.sub.3                                                                                  ##STR46##                                                                            C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              SCN violet                                54                                                                                   ##STR47##                                                                                ##STR48##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5                                              CN  reddish blue                          55   C.sub.6 H.sub.5                                                                           ##STR49##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             (C.sub.2 H.sub. 4 O).sub.2 C.sub.2 H.sub.5                                             CN  reddish blue                          56   C.sub.6 H.sub.5CH.sub.2                                                                  C.sub.6 H.sub.5                                                                       C.sub.3 H.sub.6 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5                                              CN  violet                                57   CH.sub.3 OC.sub.2 H.sub.4                                                                 ##STR50##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.3 H.sub.6 OCH.sub.3                                                              CN  navy                                  58   C.sub.2 H.sub.5 OC.sub.2 H.sub.4                                                          ##STR51##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.3 H.sub.6 OCH.sub.3                                                              CN  navy                                  59   C.sub.2 H.sub.5 OC.sub.2 H.sub.4                                                          ##STR52##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              CN  navy                                  60                                                                                   ##STR53##                                                                                ##STR54##                                                                            C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                      C.sub.2 H.sub.4 OCH.sub.3                                                              CN  reddish blue                          61                                                                                   ##STR55##                                                                                ##STR56##                                                                            C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                      C.sub.3 H.sub.6 OCH.sub.3                                                              CN  blue                                  62                                                                                   ##STR57##                                                                                ##STR58##                                                                            C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                       CN  blue                                  __________________________________________________________________________

EXAMPLE 63

A mixture of 200 g of glacial acetic acid, 50 g of propionic acid and 20 g of 96% strength by weight sulfuric acid was stirred at room temperature with 15 g of finely milled 3-methylthio-5-aminothiadiazole. It was then cooled to 1°-3° C., 32 g of 42% strength by weight nitrosylsulfuric acid were added dropwise at this temperature while cooling, and stirring was continued for 2.5 hours at from 0° to 5° C. The resulting, orange diazonium salt solution was added to a solution of 31.2 g of the thiazole of the formula ##STR59## in 35 g of glacial acetic acid, which was diluted with a mixture of 8 ml of concentrated hydrochloric acid, 300 ml of water and 1 g of amidosulfonic acid and cooled with ice to 0° C. Coupling took place completely at pH<0.8. The pH of the coupling mixture was increased to 0.3-0.5 with dilute sodium hydroxide solution and stirring was continued for 1 hour, and the precipitate was filtered off under suction, washed and dried. 46.5 g of a violet dye of the formula ##STR60## which dissolves in N,N-dimethylformamide to give a reddish blue solution were obtained

λ_(max) : 568 nm (9 : 1 v/v N,N-dimethylformamide/ glacial acetic acid).

The dye dyes polyester fabric in strong bluish violet hues having good lightfastness and fastness to heat-setting.

The dyes listed in Table 5 below are obtained in a similar manner.

                                      TABLE 5                                      __________________________________________________________________________      ##STR61##                                                                     Example No.                                                                           R.sup.1 R.sup.2    R.sup.3                                                                               R.sup.4 Hue                                   __________________________________________________________________________     64     SCH.sub.3                                                                              C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              reddish violet                        65     SCH.sub.3                                                                               ##STR62## C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              reddish blue                          66     SC.sub.2 H.sub.5                                                                        ##STR63## C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              reddish blue                          67     SCH.sub.3                                                                               ##STR64## C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.3 H.sub.6 OCH.sub.3                                                              reddish blue                          68     SCH.sub.3                                                                              C.sub.6 H.sub.5                                                                           C.sub. 3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                              violet                                69     SCH.sub.3                                                                               ##STR65## C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.3 H.sub.6 OCH.sub.3                                                              bluish violet                         70     SCH.sub.3                                                                               ##STR66## C.sub.3 H.sub.6 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                              violet                                71     SCH.sub.3                                                                              C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                     violet                                72     SCH.sub.3                                                                              C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.2 C.sub.2                                              H.sub.5 violet                                73     SCH.sub.3                                                                               ##STR67## C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.2 C.sub.2                                              H.sub.5 bluish violet                         74     SCH.sub.3                                                                               ##STR68## C.sub.2 H.sub.5                                                                       (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                     bluish violet                         75     SCH.sub.3                                                                               ##STR69## C.sub.3 H.sub.6 OCH.sub.3                                                             (C.sub.2 H.sub.4 O).sub.2 C.sub.2                                              H.sub.5 bluish violet                         76     SCH.sub.3                                                                               ##STR70## C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                      C.sub.3 H.sub.6 OCH.sub.3                                                              bluish violet                         77     CH.sub.3 O.sub.2 CC.sub.2 H.sub.4 S                                                     ##STR71## C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OCH.sub.3                                                              bluish violet                         78     CH.sub.3 O.sub.2 CC.sub.2 H.sub.4 S                                                    C.sub.6 H.sub.5                                                                           C.sub.6 H.sub.5                                                                       C.sub.3 H.sub.6 OCH.sub.3                                                              violet                                79     CH.sub.3 O.sub.2 CC.sub.2 H.sub.4 S                                                     ##STR72## C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                       bluish violet                         __________________________________________________________________________

EXAMPLE 80

13.9 g of 3-methyl-4-cyano-5-aminoisothiazole were dissolved in a mixture of 210 ml of glacial acetic acid and 50 ml of propionic acid at 50° C. The solution was then cooled to 10° C., after which 14 g of concentrated sulfuric acid and then, at from 0° to 4° C., 32 g of nitrosylsulfuric acid (45% strength by weight) were added dropwise. The mixture was stirred for 3 hours at from 0° to 5° C., after which a clear diazonium salt solution was obtained. This was run, with thorough stirring, into 30 g of the coupling component of the formula ##STR73## dissolved in a mixture, cooled to 0°-5° C., of 150 g of glacial acetic acid, 40 g of propionic acid and 0.5 g of urea. During this procedure, the temperature was kept at ≦5° C. by cooling. Thereafter, the mixture was buffered by adding sodium acetate at ≦5° C. in such a way that the free sulfuric acid was bound (pH of the mixture about 0.5-1.5). The resulting dye of the formula ##STR74## was precipitated by adding water, filtered off under suction, washed and dried. Yield: 43 g.

The dye dissolves in N,N-dimethylformamide to give a bluish red solution and dyes polyester fabric in lightfast, bluish red hues. The absorption maximum, measured in a mixture of N,N-dimethylformamide and glacial acetic acid (9 : 1 v/v), is 526 nm.

EXAMPLE 81

13.9 g of 3-methyl-4-cyano-5-aminoisothiazole were diazotized similarly to Example 80 and the product was combined with 29 g of the coupling component of the formula ##STR75## which had been dissolved in a mixture of 150 g of glacial acetic acid and 40 g of propionic acid at 2° C. Thereafter, 35 g of dry sodium acetate were sprinkled in while stirring and cooling at ≦6° C., the coupling reaction being initiated.

After the end of the reaction, the resulting dye of the formula ##STR76## was precipitated with water and was isolated similarly to Example 1. 42 g of a dark red powder were obtained, the said powder dissolving in N,N-dimethylformamide to give a pale bluish red solution and dyeing polyester fabric in bluish red hues having very good fastness properties. The UV spectrum has a virtually symmetric curve in the visible spectral range. The absorption maximum is 525 nm.

EXAMPLE 82

13.9 g of 3-methyl-4-cyano-5-aminoisothiazole were dissolved at 50° C. in a mixture of 210 ml of glacial acetic acid and 50 ml of propionic acid. The solution was then cooled to 10° C., and 14 g of concentrated sulfuric acid (96% strength by weight) were added dropwise. Thereafter, the suspension was cooled to 2°-4° C. and 32 g of nitrosylsulfuric acid (44% strength by weight) were added dropwise at this temperature. After stirring had been carried out for 3 hours, a clear diazonium salt solution was obtained. Excess nitrous acid was then destroyed with urea. The diazonium salt solution was then run into a solution of 25.0 g of the coupling component of the formula ##STR77## in 160 ml of glacial acetic acid and 40 ml of propionic acid. The solution was cooled to 2°-4° C. After the addition of the diazonium salt, the dye of the formula ##STR78## was obtained. The dye was precipitated by adding water. After the mixture had been buffered at pH 0-0.5 with sodium hydroxide solution, the dye was isolated by filtration under suction, washing with water and drying. 39.6 g of a bluish black powder were obtained, the said powder dissolving in N,N-dimethylformamide to give a reddish blue solution. The absorption maximum, measured in a mixture of N,N-dimethylformamide and glacial acetic acid (9 : 1 v/v), is 577 nm.

The dye dyes polyester fabric in reddish blue to navy hues.

Because of its good affinity to polyester fibers, it is also suitable for (sublimation) transfer printing.

The dyes listed in Tables 6, 7 and 8 below are obtained in a similar manner.

                                      TABLE 6                                      __________________________________________________________________________      ##STR79##                                                                     Example No.                                                                           R.sup.1    R.sup.5                                                                           R.sup.2   R.sup.3                                                                              R.sup.4   Hue                             __________________________________________________________________________     83     CH.sub.3   SCN                                                                                ##STR80##                                                                               C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                red                             84     CH.sub.3   CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                      85     CH.sub.3   CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                                bluish red                      86     CH.sub.3   CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 bluish red                      87     C.sub.2 H.sub.5                                                                           CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 bluish red                      88     C.sub.3 H.sub.5                                                                           CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                                bluish red                      89     C.sub.2 H.sub.5                                                                           CN                                                                                 ##STR81##                                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 bluish red                      90     CH.sub.3   CN                                                                                 ##STR82##                                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 bluish red                      91     CH.sub.3   Cl                                                                                 ##STR83##                                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 yellowish red                   92     CH.sub.3   Br                                                                                 ##STR84##                                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 yellowish red                   93     C.sub.6 H.sub.5                                                                           CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub. 4                                              OCH.sub.3 bluish red                      94                                                                                     ##STR85## CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 bluish red                      95     CH.sub.3 OC.sub.2 H.sub.4                                                                 CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4                                               OCH.sub.3 bluish red                      96     CH.sub.3 OC.sub.2 H.sub.4                                                                 CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OCH.sub.3                                                                bluish red                      97     CH.sub.3 OC.sub.2 H.sub.4                                                                 CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                      98     CH.sub.3 (OC.sub.2 H.sub.4).sub.2                                                         CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                          bluish red                      99     C.sub.2 H.sub.5 (OC.sub.2 H.sub.4).sub.2                                                  CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                          bluish red                      100    C.sub.2 H.sub.5 (OC.sub.2 H.sub.4).sub.2                                                  CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub. 3 H.sub.6 OCH.sub.3                                                               bluish red                      101                                                                                    ##STR86## CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                          bluish red                      102                                                                                    ##STR87## CN CH.sub.2 OC.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                      103    CH.sub.3 (OC.sub.2 H.sub.4).sub.2                                                         CN                                                                                 ##STR88##                                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                          dull bluish                     __________________________________________________________________________                                                    red                        

                                      TABLE 7                                      __________________________________________________________________________      ##STR89##                                                                     Example No.                                                                           R.sup.1       R.sup.3                                                                              R.sup.4   Hue                                       __________________________________________________________________________     104    CH.sub.3      C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OCH.sub.3                                                                red                                       105    CH.sub.3      CH.sub.3                                                                             C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                                106    CH.sub.3      C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                                107    CH.sub.3      C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         bluish red                                108    CH.sub.3      C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                                109    CH.sub.3      C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish red                                110    C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish red                                111    CH.sub.3 OC.sub.2 H.sub.4                                                                    C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OCH.sub.3                                                                bluish red                                112    CH.sub.3 OC.sub.2 H.sub.4                                                                    C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                                113    C.sub.6 H.sub.5                                                                              C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish red                                114                                                                                    ##STR90##    C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish red                                115                                                                                    ##STR91##    C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                          bluish red                                116                                                                                    ##STR92##    C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OCH.sub.3                                                                bluish red                                117                                                                                    ##STR93##    C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                bluish red                                118    CH.sub.3 (OC.sub.2 H.sub.4).sub.2                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                          bluish red                                119    CH.sub.3 OC.sub.2 H.sub.4                                                                    C.sub. 2 H.sub.5                                                                     C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6                                      H.sub.5   bluish red                                120    CH.sub.3      C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6                                      H.sub.5   bluish red                                121    CH.sub.3 OC.sub.2 H.sub.4                                                                    CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                            bluish red                                122    CH.sub.3 (OC.sub.2 H.sub.4).sub.2                                                            CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                            bluish red                                123                                                                                    ##STR94##    C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish red                                __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________      ##STR95##                                                                     Example No.                                                                           R.sup.1     R.sup.2    R.sup.3   X     n λmax                    __________________________________________________________________________                                                     [nm]                           124    C.sub.2 H.sub.5 (OC.sub.2 H.sub.4).sub.2                                                   C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.5                                                                          CCN   0 554                            125    C.sub.2 H.sub.5 (OC.sub.2 H.sub.4).sub.2                                                    ##STR96## C.sub.2 H.sub.5                                                                          CCN   0 581                            126    C.sub.6 H.sub.5 CH.sub.2 OC.sub.2 H.sub.4                                                   ##STR97## C.sub.2 H.sub.5                                                                          CCN   0 581                            127    C.sub.6 H.sub.5 (OC.sub.2 H.sub.4).sub.2                                                    ##STR98## C.sub.2 H.sub.5                                                                          CCN   0 580                            128    C.sub.2 H.sub.5 OC.sub.2 H.sub.4                                                           C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.4 CN                                                                       CCN   1 544                            129                                                                                    ##STR99##  C.sub.6 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                                CCN   0 552                            130    CH.sub.3 OC.sub.2 H.sub.4                                                                  C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.4 CN                                                                       CCN   1 544                            131    C.sub.6 H.sub.5                                                                            C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.4 CN                                                                       CCN   1 552                            132    CH.sub.3                                                                                    ##STR100##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 C.sub.6                                     H.sub.5   CCN   0 581                            133    CH.sub.3 OC.sub.2 H.sub.4                                                                   ##STR101##                                                                               C.sub.2 H.sub.4 OCH.sub.3                                                                CCN   0 569                            134    NCC.sub.2 H.sub.4 S                                                                        C.sub.6 H.sub.5                                                                           C.sub.2 H.sub.5                                                                          N     0 540                            135    NCC.sub.2 H.sub.4 S                                                                         ##STR102##                                                                               C.sub.2 H.sub.5                                                                          N     0 565                            136    CN                                                                                          ##STR103##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 C.sub.2                                     H.sub.5   CCN   0 578                            137    NCC.sub.2 H.sub.4 S                                                                        C.sub.6 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                                N     0 537                            138    CN                                                                                          ##STR104##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 C.sub.2                                     H.sub.5   CCN   0 595                            139    CH.sub.3 OC.sub.2 H.sub.4                                                                   ##STR105##                                                                               C.sub.3 H.sub.6 OCH.sub.3                                                                CCN   0 528                            140                                                                                    ##STR106##                                                                                 ##STR107##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                              CCN   0 592                            141                                                                                    ##STR108##                                                                                 ##STR109##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                              CCN   0 588                            142                                                                                    ##STR110##                                                                                 ##STR111##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3                                              CCN   0 581                            143    Cl                                                                                          ##STR112##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                              CCN   0 592                            144    Cl                                                                                          ##STR113##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 C.sub.2                                     H.sub.5   CCN   0 592                            145                                                                                    ##STR114##                                                                                 ##STR115##                                                                               C.sub.2 H.sub.4 OCH.sub.3                                                                CCN   0 590                            146                                                                                    ##STR116##                                                                                 ##STR117##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 C.sub.2                                     H.sub.5   CCN   0 584                            147                                                                                    ##STR118##                                                                                 ##STR119##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                              CCN   0 589                            148                                                                                    ##STR120##                                                                                 ##STR121##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                              CCN   0 590                            149                                                                                    ##STR122##                                                                                 ##STR123##                                                                               CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                              CCN   0 590                            __________________________________________________________________________ 

We claim:
 1. A thiazoleazo dye of the formula I ##STR124## wherein X is a radical C--R⁵, R⁵ being cyano, halogen, C₁ -C₄ -alkoxycarbonyl or thiocyanato,R¹ is phenyl, phenyl substituted C₁ -C₆ -alkoxy, sulfamoyl or C₁ -C₄ -mono- and dialkylsulfamoyl, C₁ -C₄ -mono and dialkylsulfamoyl where the alkyl chain is interrupted by an oxygen atom, furyl, thienyl, C₁ -C₄ -alkylthienyl, halothienyl or pyridyl, R² is phenyl, or thienyl, R³ is C₁ -C₄ -alkyl, or C₃ -C₁₂ -alkyl whose alkyl chain is interrupted by from 1 to 4 oxygen atoms, and R⁴ is C₃ -C₈ -alkyl whose alkyl chain is interrupted by from 1 to 4 oxygen atoms.
 2. A thiazoleazo dye as claimed in claim 1, wherein R⁵ is cyano.
 3. The thiazoleazo dye according to claim 1, of the formula ##STR125##
 4. The thiazoleazo dye according to claim 1, of the formula ##STR126## 